2¾ 2¾ A7 B7 !修正 i補先 五、 發明說明(1 (2001年12月修正） 發明領域 (請先閱讀背面之注意事項再填寫本頁) 本發明關於一種製備一聚矽氧烷醯亞胺-矽石混成物 的方法。特別地，關於利用一內含利用帶有兩端含矽烷的 聚醯胺酸及四甲氧基矽烷的混合物來製備聚矽氧烷醯亞 胺-矽石混成物的方法。 發明背景 有機-無機混成材料因具有極佳的透明度、耐磨耗、 耐熱等特性，具潛在廣泛的應用領域，其中包括在塗料、 光學材料、電子元件及生醫材料的應用，因爲此材料兼具 了有機及無機材料的特性，所以被應用於同時具有有機及 無機成份之產品時將更能顯現出其優越的特性。有機-無機 混成材料在工業上之應用，又以保護性塗料方面的可行性 較高，例如具備防污、防水功能之室內外建材之塗裝，金 屬的防蝕塗膜等。然而，最能凸顯有機-無機混成材料特性 之應用則屬在光學用透明薄膜之應用，這包括鏡片及車窗 耐磨功能的提升，若經適當之設計更可賦與這些薄膜防 霧、撥水及抗反射等功能。 經濟部智慧財產局員工消費合作社印製 聚醯亞胺由於優良的機械性質、耐火性質、尺寸安 定性質和低介電常數，在電絕緣、微電子和黏著劑之應用 上極爲普遍，但由於聚醯亞胺具有較高的吸水性（〜4重量 %)及熱膨脹係數（〜50 ppm/K)，而阻礙其在電子材料上的 應用。相反地，矽石（Silica)具有非常低的吸水性（〜0重量 %)及熱膨脹係數（〜0.5 ppm/K)，使其較適合於電子材料上 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） B7 五、發明説明（） 2 (請先閲讀背面之注意事項再填寫本頁) 的應用，但是其介電性質及尺寸安定性質卻不如聚醯亞 胺。聚醯亞胺-矽石混成材料則是取其兩者之優點互補其缺 點，使其在材料上的應用更具優越性。高分子改質可經由 塊狀共聚合（block copolymerization)、接枝共聚合（graft copolymerization)、摻合（blend)、互穿透高分子網 (interpenetrating polymer network ; IPN)、混成（hybrids) 及複合材料化（composites)等方式達到。許多的硏究利用 溶膠-凝膠合成方法將無機氧化物摻入有機聚合物中，製備 高均勻相的有機-無機混成材料，且其結構與特性和製程有 密切地關係。 經濟部中央標準局員工消費合作社印製 最早有關聚醯亞胺_矽石（P卜Si02)混成物的硏究報 告是在 1990 年 Nandi 等人[Nandi, M·; Conklin, J. A.; Salviati, J.L; Sen, A. ChemMater，1990,2,772]，利用苯 四甲酸二酐（pyromelHtic anhydride)、二胺基二苯基乙醚 (diaminodiphenyl ether)及四甲氧砂院合成P卜Si〇2，討論 有機-無機相之間的作用力及相分離現象。Morikawa等人 [Morikawa, A.; lyoku, Y.; Kakimoto, Μ;, Imai, Y.J Mater Chem，1992, 2, 679 及 Morikawa，A·; lyoku, Υ·; Kakimoto, M，; Imai，Y. Polym J，1 992，24，107]，合成在聚醯亞胺 主幹鏈上的矽氧烷與矽石（Si02)形成化學鍵結，結果發現 聚醯亞胺鏈段的移動性受到阻礙。另外，Mascia等人 [Mascia, L.; Kioul, A. J Mater Sci Lett 1994, 175, 169.] 及 Wang 等人[Wang, S_; Ahmad, Z·; Mark, J.E. Macro mol Rep 1994，A31, 411 和 Wang, S; Ahmad，Z; Mark，J.E_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 483909 修正ma 本派漆^ A7 B7 五、發明說明（3 ) (2001年12月修正)2¾ 2¾ A7 B7! Amendment 5 First, the description of the invention (1 (revised in December 2001) Field of invention (please read the precautions on the back before filling this page) The present invention relates to a method for preparing a polysiloxane -Silica mixture method. In particular, it is related to the preparation of a polysiloxane-imide-silica mixture by using a mixture of polyamidoacid and tetramethoxysilane containing silane at both ends. BACKGROUND OF THE INVENTION Organic-inorganic hybrid materials have potential for a wide range of applications due to their excellent transparency, abrasion resistance, and heat resistance, including applications in coatings, optical materials, electronic components, and biomedical materials, because This material has the characteristics of both organic and inorganic materials, so when it is applied to products with both organic and inorganic components, it will show its superior characteristics. Organic-inorganic hybrid materials are industrially applied with protective properties. The feasibility of coatings is high, such as the coating of indoor and outdoor building materials with anti-fouling and waterproof functions, metal anti-corrosion coatings, etc. However, it can best highlight the characteristics of organic-inorganic hybrid materials. The application is in the application of optical transparent film, which includes the improvement of the wear resistance of lenses and windows. If properly designed, these films can be given anti-fog, water repellency and anti-reflection functions. Intellectual Property of the Ministry of Economic Affairs Bureau's consumer cooperatives printed polyimide. Because of its excellent mechanical properties, fire resistance, dimensional stability, and low dielectric constant, it is extremely common in electrical insulation, microelectronics, and adhesive applications. High water absorption (~ 4% by weight) and thermal expansion coefficient (~ 50 ppm / K) hinder its application in electronic materials. In contrast, Silica has very low water absorption (~ 0 weight %) And thermal expansion coefficient (~ 0.5 ppm / K), making it more suitable for electronic materials. The paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) B7 V. Description of the invention () 2 (Please First read the notes on the back before filling out this page), but its dielectric properties and dimensional stability are not as good as polyimide. Polyimide-silica hybrid materials are based on the advantages of the two and complement their disadvantages. ,Make Its application in materials is more superior. Polymer modification can be through block copolymerization (graft copolymerization), graft copolymerization (graft copolymerization), blending (blend), interpenetrating polymer network (interpenetrating polymer) network; IPN), hybrids and composites, etc. Many studies have used sol-gel synthesis to incorporate inorganic oxides into organic polymers to prepare highly homogeneous organic-inorganic Hybrid materials, and their structure and characteristics are closely related to the manufacturing process. The earliest research report on polyimide-silica (Pb Si02) mixtures printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs was in Nandi in 1990. Et al. [Nandi, M .; Conklin, JA; Salviati, JL; Sen, A. ChemMater, 1990, 2,772], using pyromelHtic anhydride, diaminodiphenyl ether, and Tetramethoxyacetate synthesizes PbO2 and discusses the interaction between organic and inorganic phases and the phenomenon of phase separation. Morikawa et al. [Morikawa, A .; lyoku, Y .; Kakimoto, Μ ;, Imai, YJ Mater Chem, 1992, 2, 679 and Morikawa, A ·; lyoku, Υ ·; Kakimoto, M ,; Imai, Y. Polym J, 1 992, 24, 107]. Siloxane synthesized on the backbone of polyimide forms a chemical bond with silica (Si02). As a result, it is found that the mobility of the polyimide segment is hindered. In addition, Mascia et al. [Mascia, L .; Kioul, A. J Mater Sci Lett 1994, 175, 169.] and Wang et al. [Wang, S_; Ahmad, Z ·; Mark, JE Macro mol Rep 1994, A31, 411 and Wang, S; Ahmad, Z; Mark, J.E_ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 483909 Correction ma Benpai ^ A7 B7 V. Description of the invention (3) (2001) (Amended in December)
Chem MateM994, 6, 943·]則進一步在形成化學鍵結的矽 (請先閱讀背面之注意事項再填寫本頁) 氧烷與矽石混成物中添加鍵結劑（Bonding agent)，藉以提 昇混成材料之機械強度及安定性。Gaw等人[Gaw, K.; Suguki, H; Jikei, M.; Kakimoto, M.; Imai, Y. Mat. Res. Soc. Symp. Proc· 1996 4^ 465]使用高壓溶膠-凝膠熱聚 合方法合成聚醯亞胺-矽石混成物，藉由改變聚醯亞胺/四 甲氧基矽烷（TMOS)比例，探討混成物的化學性質、物理性 質及熱安定性。結果發現矽氧烷均勻分佈在混成物中，且 有兩種明顯不同的硬度。另外，Goizet等人[Goizet, S.; Schrotter, J.C.; Smaihi, M.; Deratani, A. New J. Chem. 經濟部智慧財產局員工消費合作社印製 1 997 2± 46 1】亦使用溶膠-凝膠方法製備聚醯亞胺-矽石混 成物薄膜，探討不同的矽含量、水含量及表面微結構。另 ^ ^lL^[J^®Yabe [JP62-2 32 1 47]¾ lijima [JP07-86736] 在聚醯亞胺中摻混一層Si02粉，以阻絕濕氣進入聚醯亞胺 中，而Toyoshima等人[JP05-51 541]則以含有Si(OR)3基之 聚醯亞胺包覆Si〇2粉使在半導體中。雖然，由近幾年發表 文獻彙整分析，使用溶膠-凝膠方法已經成功製備聚醯亞胺 -矽石混成物，但是所製得聚醯亞胺-矽石混成物多具有嚴 重的相分離問題，且該相分離問題會更進一步地影響所製 成混成物的機械性質及熱性質。 本發明的目的在提供一種製備具化學鍵結互穿網型 聚矽氧烷醯亞胺-矽石（9〇~31丨0\3叩^丨€^-31丨丨03)混成物 高分子結構體的方法。利用該方法能製備具有低的相分離 現象的聚矽氧烷醯亞胺-矽石混成物。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4^3909Chem MateM994, 6, 943 ·] will further add chemical bonding silicon (please read the precautions on the back before filling in this page). Bonding agent is added to the mixture of oxane and silica to improve the mixed material. Mechanical strength and stability. Gaw et al. [Gaw, K .; Suguki, H; Jikei, M .; Kakimoto, M .; Imai, Y. Mat. Res. Soc. Symp. Proc. 1996 4 ^ 465] using high pressure sol-gel thermal polymerization Methods A polyimide-silica mixture was synthesized, and the chemical, physical, and thermal stability of the mixture was discussed by changing the ratio of polyimide / tetramethoxysilane (TMOS). It was found that the siloxane was uniformly distributed in the mixture and had two significantly different hardnesses. In addition, Goizet et al. [Goizet, S .; Schrotter, JC; Smaihi, M .; Deratani, A. New J. Chem. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 997 2 ± 46 1] also used sol- The polyimide-silica mixed film was prepared by the gel method, and the different silicon content, water content, and surface microstructure were discussed. Another ^ lL ^ [J ^ ®Yabe [JP62-2 32 1 47] ¾ lijima [JP07-86736] Blend a layer of SiO2 powder in polyimide to prevent moisture from entering the polyimide, and Toyoshima [JP05-51 541] et al. Coated Si02 powder with poly (imide) containing Si (OR) 3 group and used it in semiconductors. Although published literature analysis in recent years, the polyimide-silica mixture has been successfully prepared using the sol-gel method, but most of the polyimide-silica mixtures produced have serious phase separation problems. Moreover, the phase separation problem will further affect the mechanical and thermal properties of the resulting mixture. The object of the present invention is to provide a polymer structure having a chemically bonded interpenetrating network type polysiloxane-imide-silica (90 ~ 31 丨 0 \ 3 叩 ^ €€ -31 丨 丨 03) mixture. Body method. By this method, a polysiloxane-imine-silica mixture having a low phase separation phenomenon can be prepared. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 4 ^ 3909
A7 B7 (2001年12月修正) 發明要旨 (請先閲讀背面之注意事項再填寫本頁) 本發明揭示一種製備互穿網型聚矽氧烷醯亞胺-矽石 混成物的方法，其包含下列步驟： a) 製備一具有兩端含矽烷的化學式I之結構的聚醯胺 酸的有檄溶液， ?Xl Η 0 OH Η ο Ο Η ?Χι Χ3— Si -fCH^^N—^~ΑΐΓγ-ΐ~ Ν-Αγ2 - Ν A— b~Ar^6- N-(CH2"^Si — Χ3 ΟΧ2 ΗΟ06 COOH ΗΟ〇6 COOH 6)^ (化學式l) 其中AM、Ar2的定義如前所述； m爲1〜5的整數：及 Xi，X2，X3獨立地爲甲基或乙基； b) 將四甲氧基矽烷的一有機溶液與水分別加入步驟a) 所得之具有兩端含矽烷的聚醯胺酸的有機溶液，形成一混 合物；以及 經濟部智慧財產局員工消費合作社印製 c)加熱步驟b)所得之混合物，使得化學式I的聚醯胺 酸進行熱環化反應，形成醯亞胺結構，同時使得四甲氧基 矽烷及化學式丨的聚醯胺酸的烷氧基水解及聚縮合而形成 一f_Si-0十結構，於是獲得一聚矽氧烷醯亞胺-矽石混成 物。 於本發明所亦揭示的方法的步驟a)中’優選地’該有 機溶液的製備係藉由將一溶於有機溶劑的二胺與一溶於 有機溶劑的二酸酐反應，再加入溶於有機溶劑一計量的胺 基二烷氧基矽烷來進行，其中 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 483909 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（5 ) _1年12月修正)A7 B7 (Amended in December 2001) Summary of the invention (please read the precautions on the back before filling out this page) The present invention discloses a method for preparing an interpenetrating mesh type polysiloxane-imine-silica mixture, which comprises The following steps: a) Prepare a fluorinated solution of a polyphosphonic acid having the structure of silane containing chemical silane I at both ends,? Xl Η 0 OH ο ο Ο Η? Χ3—Si -fCH ^^ N— ^ ~ ΑΐΓγ -ΐ ~ Ν-Αγ2-Ν A— b ~ Ar ^ 6- N- (CH2 " ^ Si — χ3 Οχ2 ΗΟ06 COOH Η〇〇6 COOH 6) ^ (Chemical Formula l) wherein the definitions of AM and Ar2 are as described above; m is an integer from 1 to 5: and Xi, X2, and X3 are independently methyl or ethyl; b) an organic solution of tetramethoxysilane and water are separately added to step a) An organic solution of polyamic acid to form a mixture; and printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs c) heating the mixture obtained in step b), so that the polyamic acid of chemical formula I undergoes a thermal cyclization reaction to form rhenium Amine structure, at the same time the tetramethoxysilane and the polyalkanoic acid of the chemical formula 丨 alkoxy hydrolysis and polycondensation to form f_Si-0 ten structure, thereby obtaining a silicon oxide alkanoyl polyethylene imine - Silica hybrid thereof. In step a) of the method also disclosed in the present invention, it is preferred that the organic solution is prepared by reacting a diamine dissolved in an organic solvent with a dianhydride dissolved in an organic solvent, and then adding a solution dissolved in an organic solvent. Solvent is measured by measuring the amount of aminodialkoxysilane, in which the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 483909 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention ( 5) _1 December correction)
該二胺爲 其中Ar2的定義如前所述；及 該胺基二烷氧基矽烷爲 ， X3-Si -fCH2^NH2 0X2 其中m、X1、X2、X3的定義如前所述。 於本發明中，優選地，該四甲氧基矽烷對該聚醯胺 酸的重量百分率介於10重量％至80重量％的範圍。優 選地，該水對該四甲氧基矽烷的莫耳比介於3至1 0之間 的範圍。優選地，該有機溶液係使用一選自由N-甲基-2-吼略院酮（N-methy 卜 2-pyrrolidone; NMP)、N，N-二甲基乙 醯胺（1^,1^-(1丨016化乂130613阳丨€16;01\/1八0)、二甲基甲醯胺 (dimethylformamide; DMF)、二甲亞碼（dimethylsulfoxide; DMS〇）、m-甲酉分（m_cresol)、口比 n定（pyridine; Py)、氯化甲 烷、氯化乙院.及其組合所組成族群的有機溶劑。 圖示之簡單說明 圖1顯示本發明互穿網型混成物的一較佳實施例的 製備流程圖。 圖2顯示由圖1所示流程製得的互穿網型混成物的 理論結構圖。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — — — — — — — — — ^ ·1111111 a — — — — — — — — (請先閱讀背面之注意事項再填寫本頁) 483909 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（） 6 圖3顯示由圖1所示流程製得的互穿網型混成物的 富利葉轉換紅外線光譜圖（FTIR)，其中（A)樣品6A，（B)樣 品 6A-30，（C)樣品 6A-50，（D)樣品 6A_70，（E)樣品 8A-50，（F)樣品 10A-50。 圖4顯示由圖1所示流程製得的互穿網型混成物的 29矽CP/MAS核磁共振光譜圖，其中（A)樣品6A，（B)樣品 6A-3 0，（C)樣品 6A-50，（D)樣品 6A-70，（E)樣品 8A-50， (F)樣品 10A-50。 圖5顯示由圖1所示流程製得的互穿網型混成物的 空氣下熱重損失分析圖，其中（A)樣品6A，（B)樣品6A-30， (C)樣品 6A-50，（D)樣品 6A-70，（E)樣品 8A-50，（F)樣品 10A-50。 圖6顯示由圖1所示流程製得的互穿網型混成物的 氮氣下熱重損失分析圖，其中（A)樣品6A，（B)樣品6A-30， (C)樣品 6A-50，（D)樣品 6A-70，（E)樣品 8A-50，（F)樣品 10A-50。 較佳實施例及詳細說明 實施例 製備具化學鍵結的互穿網型高分子結構體的聚矽氧 烷醯亞胺-矽石混成物所使用之反應物的重量與混合溶劑 體積比爲20 %(w/v)。氮氣下在250毫升的圓底瓶中，加 入適量的3,3'，4,4'_二苯酮四甲酸二酐（3,3'4·-benzophenone tetracarboxylic dianhydride; BTDA)的 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） !裝--------訂---------線J (請先閱讀背面之注意事項再填寫本頁) B7 1、發明說明（7 ) (請先閱讀背面之注意事項再填寫本頁) 叱1^-二甲基乙醯胺（问屮-€1丨11^化7130613阳1€16;01\/1八0)溶液 攪拌之。計量的苯二胺（Oxydianiline; ODA)的Ν，Ν·二甲 基乙醯胺溶液（ODA + DMAc)緩慢地加入圓底瓶中，反應30 分鐘。再將計量的矽氧烷[3-胺基丙基甲基二氧乙基矽烷 (3-aminopropylmethyldiethoxysilane; APrMDEOS)]力口入 反應系統中，與未反應之酸酐基團反應，形成一淸徹混合 物。該混合物在室溫下反應24小時後，形成一帶有兩含 矽烷末端的聚醯胺酸的溶液。在該溶液中加入四甲氧矽烷 (Tetramethoxysilane; TM0S)的 N，N-二甲基乙醯胺（N，N-dimethylacetamide; DMAc)溶液，隨後再添加去離子水， 在室溫下反應24小時形成一聚醯胺酸-矽石均勻溶液。隨 後，將該均勻溶液倒入鐵氟龍燒杯置於60°C烘箱中24小 時，然後取出烘乾之薄膜再減壓真空加熱1 00°C 3小時、 經濟部智慧財產局員工消費合作社印製 2 00〇C 3小時、250〇C 2小時、300〇C 2小時，形成互穿網型 聚矽氧烷醯亞胺-矽石混成物。上述過程中，以三種不同的 水解比例（[H20]/[TM0S]莫耳比；水/四甲氧矽烷莫耳 比）6、8和10所製得的成品分別地表示爲6A、8A及10A。 6A-30、6A-50和6A-70的樣品，分別地表示在水解比例 [H20]/[TM〇S] = 6的條件下分別與30%、50%和70%的四 甲氧矽烷反應所得之混成物。合成反應條件如表1所示， 實驗流程如圖1所示。該混成物以IR光譜、NMR光譜、 DSC及TGA等儀器加以分析。 該混成物的醯亞胺化及聚縮合反應利用FTIR (Bomen DA 3.002)來鑑定，同時分析醯亞胺鏈上的羰基 -10 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 483909 A7 .—__B7_ 丨 五、發明說明（8 ) (c = 0)與矽石（Si02)網狀結構上的羥基（0-H)之間的氫鍵 作用力。矽膠具有高表面積結構，與矽烷耦合劑鍵結形成 網狀結構後，可利用固態29Si CP/MAS NMR(Bruker MSL-400)交叉極化（cross-polarization)方法結合 magicangle spinning(CP/MAS)和高能量去偶合技術，來 硏究混成物界面結構及相行爲。矽烷氧化矽（silicon alkoxide)在水解聚縮合過程中矽原子吸收峰約爲-90、-100及-110ppm，定義爲Q2、Q3及Q4，如下所示： Q2 = (R〇)2Si(OSi)2，Q3 = ROSi(OSi)3，Q4 = Si(OSi)4，R = H 或烷基。若具有二個有機側鏈的矽烷耦合劑本身鍵結形成 網狀結構則定義爲Dj(i = 1或2)，如下所示： D1 = ROSi(OSi)R'2, D2 = Si(OSi)2R'2(圖 2)。 表1聚矽氧烷醯亞胺-矽石混成物合成反應組成 ~ BTDA ODA~APrIVIDEOS~TMOS~H20/T1\/I0S SiOo3 …一 … (m mm/〇)麵u 6A 0.024 0.012 0.024 0 * 7 6A-30 0.024 0.012 0.024 30 6 23 6A-50 0.024 0.012 0.024 50 6 35 6A-70 0.024 0.012 0.024 70 6 47 8A-50 0.024 0.012 0.Q24 50 8 35 10Ah50 0.024 0.012 0.024 50 10 36 1口入與6A-30相同含量的水。 1在空氣中加熱至800°C時的殘餘量爲矽含量 -1 1 - 參I氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------裝--------訂---------線丨 (請先閱讀背面之注意事項再填寫本頁) 4秦 A7The diamine is wherein the definition of Ar2 is as described above; and the amine dialkoxysilane is and X3-Si-fCH2 ^ NH2 0X2 wherein m, X1, X2, and X3 are defined as described above. In the present invention, preferably, the weight percentage of the tetramethoxysilane to the polyamic acid is in the range of 10% to 80% by weight. Preferably, the molar ratio of the water to the tetramethoxysilane is in the range of 3 to 10. Preferably, the organic solution uses a compound selected from N-methy-2-pyrrolidone (NMP), N, N-dimethylacetamide (1 ^, 1 ^ -(1,016,130,130,613,16; 01 \ / 180), dimethylformamide (DMF), dimethylsulfoxide (DMS〇), m-formamidine ( m_cresol), mouth ratio n (pyridine; Py), methane chloride, ethyl chloride, and the organic solvents of their group. Simple illustration of the figure Figure 1 shows one of the interpenetrating mesh type mixtures of the present invention. The preparation flow chart of the preferred embodiment. Figure 2 shows the theoretical structure diagram of the interpenetrating mesh type blend produced by the process shown in Figure 1. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) — — — — — — — — — — — — — ^ · 1111111 a — — — — — — — — (Please read the notes on the back before filling out this page) 483909 Employee Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Printed A7 B7 V. Description of the invention (6) Fig. 3 shows the Fourier transform infrared of the interpenetrating mesh type mixture produced by the process shown in Fig. 1 Spectrogram (FTIR), of which (A) sample 6A, (B) sample 6A-30, (C) sample 6A-50, (D) sample 6A_70, (E) sample 8A-50, (F) sample 10A-50 Figure 4 shows the 29 silicon CP / MAS NMR spectrum of the interpenetrating mesh mixture prepared by the process shown in Figure 1, where (A) sample 6A, (B) sample 6A-3 0, (C) sample 6A-50, (D) Sample 6A-70, (E) Sample 8A-50, (F) Sample 10A-50. Figure 5 shows the interpenetrating mesh type mixture produced by the process shown in Figure 1 under air heating. Weight loss analysis chart, in which (A) sample 6A, (B) sample 6A-30, (C) sample 6A-50, (D) sample 6A-70, (E) sample 8A-50, (F) sample 10A- 50. Figure 6 shows the thermogravimetric loss analysis of the interpenetrating mesh-type mixture prepared under the flow shown in Figure 1, under nitrogen (A) sample 6A, (B) sample 6A-30, (C) sample 6A- 50, (D) Samples 6A-70, (E) Samples 8A-50, (F) Samples 10A-50. Preferred Embodiments and Detailed Examples The preparation of polymer chains with chemically-bonded interpenetrating network-type polymer structures The weight ratio of the reactants used in the siloxane-imine-silica mixture to the mixed solvent volume is 20% ( w / v). Under nitrogen, add an appropriate amount of 3,3 ', 4,4'_benzophenonetetracarboxylic dianhydride (BTDA) to a 250ml round bottom bottle. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 x 297 mm)! Packing -------- Order --------- Line J (Please read the precautions on the back first Fill out this page again) B7 1. Description of the invention (7) (Please read the notes on the back before filling out this page) 叱 1 ^ -Dimethylacetamide (Ask for-€ 1 丨 11 ^ Chem 7130613 Yang 1 € 16; 01 \ / 180)) the solution was stirred. A metered amount of N, N · dimethylacetamide solution (ODA + DMAc) of phenylenediamine (Oxydianiline; ODA) was slowly added to the round-bottomed flask and reacted for 30 minutes. Then a metered amount of siloxane [3-aminopropylmethyldiethoxysilane (APrMDEOS)] was forced into the reaction system and reacted with the unreacted anhydride group to form a complete mixture. . After the mixture was reacted at room temperature for 24 hours, a solution with two siloxane-containing polyamines was formed. To this solution was added a solution of Tetramethoxysilane (TMOS) in N, N-dimethylacetamide (N, N-dimethylacetamide; DMAc), followed by deionized water, and the reaction was performed at room temperature for 24 hours. A homogeneous polyamic acid-silica solution was formed. Subsequently, the homogeneous solution was poured into a Teflon beaker and placed in an oven at 60 ° C for 24 hours, and then the dried film was removed and heated under reduced pressure and vacuum at 100 ° C for 3 hours. It was printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 hours at 2000 ° C, 2 hours at 250 ° C, and 2 hours at 300 ° C, forming an interpenetrating network type polysiloxane-imide-silica mixture. In the above process, the finished products prepared with three different hydrolysis ratios ([H20] / [TM0S] mole ratio; water / tetramethoxysilane mole ratio) 6, 8 and 10 are respectively expressed as 6A, 8A and 10A. The samples of 6A-30, 6A-50 and 6A-70 respectively react with 30%, 50% and 70% of tetramethoxysilane under the conditions of hydrolysis ratio [H20] / [TM〇S] = 6 respectively. The resulting mixture. The synthetic reaction conditions are shown in Table 1, and the experimental procedure is shown in Figure 1. The mixture was analyzed by instruments such as IR spectrum, NMR spectrum, DSC and TGA. The fluorene imidization and polycondensation reaction of this mixture were identified by FTIR (Bomen DA 3.002), and the carbonyl group on the fluorene imine chain was analyzed at the same time.-This paper is in accordance with China National Standard (CNS) A4 (210 X 297) (Mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 483909 A7 .—__ B7_ 丨 V. Description of the invention (8) (c = 0) and hydroxyl (0-H) on the network structure of silica (Si02) Hydrogen bonding force. Silicone has a high surface area structure. After bonding with a silane coupling agent to form a network structure, the solid-state 29Si CP / MAS NMR (Bruker MSL-400) cross-polarization method can be used in combination with magicangle spinning (CP / MAS) and High-energy decoupling technology to study the interface structure and phase behavior of the mixture. The silicon atom absorption peaks of silicon alkoxide during hydrolysis polycondensation are about -90, -100, and -110 ppm, which are defined as Q2, Q3, and Q4, as shown below: Q2 = (R〇) 2Si (OSi) 2, Q3 = ROSi (OSi) 3, Q4 = Si (OSi) 4, R = H or alkyl. If the silane coupling agent with two organic side chains is bonded to form a network structure, it is defined as Dj (i = 1 or 2), as shown below: D1 = ROSi (OSi) R'2, D2 = Si (OSi) 2R'2 (Figure 2). Table 1 Synthetic reaction composition of polysiloxane-imide-silica mixture ~ BTDA ODA ~ APrIVIDEOS ~ TMOS ~ H20 / T1 \ / I0S SiOo3… one ... (m mm / 〇) plane u 6A 0.024 0.012 0.024 0 * 7 6A-30 0.024 0.012 0.024 30 6 23 6A-50 0.024 0.012 0.024 50 6 35 6A-70 0.024 0.012 0.024 70 6 47 8A-50 0.024 0.012 0.Q24 50 8 35 10Ah50 0.024 0.012 0.024 50 10 36 1 mouth and 6A -30 water of the same content. 1 Residual content when heated to 800 ° C in air is silicon content -1 1-The I-scale is applicable to China National Standard (CNS) A4 (210 X 297 mm) --------- ---- Install -------- Order --------- Line 丨 (Please read the precautions on the back before filling this page) 4 秦 A7
五、發明說明（9 ) (2001年12月修正) 互穿網型混成物結構分析 (請先閱讀背面之注意事項再填寫本頁) 互穿網型聚矽氧烷醯亞胺-矽石混成物理論結構如圖2 所示。混成物6A中每個矽原子上鍵結兩個矽氧烷鍵及一個 甲烷基，形成二度空間的網狀結構（Dj ; i=1或2)。其他混 成物則因四甲氧基矽烷加入後，3-胺基丙基甲基二氧乙基 矽烷與四甲氧基矽院在水解過程中所形成的矽烷醇基（Si-〇H)，進一步聚縮合形成三度空間的網狀結構（D2及Qh 2 9 i = 2,3,4)，其結果可由FTIR及 Si NMR光譜圖獲得證實。 圖3爲不同四甲氧基矽烷及水含量之混成物FT-IR(KB〇光譜圖。結果所有混成物均出現醯亞胺特性吸收 峰：1778 cm_1(醯亞胺C = 0對稱拉伸振動），1718 cm_1 (醯 亞胺C =〇非對稱拉伸振動），1500 crn^(苯環吸收峰）， 經濟部智慧財產局員工消費合作社印製 1 382cm_1(C-N 拉伸振動），1080 cnrT1(Si-0-Si 環狀非對稱 拉伸振動），720 crrT1(醯亞胺C = 0出平面彎曲振動）。而 圖中在3200-3700 cm 1及950 cm 1兩處吸收峰，說明 八卩「1\^已〇&上的_引〇(^3與四甲氧基矽烷水解形成矽烷醇 基（-SiOH)，而-SiOH基加熱後進一步水解形成3卜0-Si( 1080 crrT1)鍵。因此推斷當混成物反應時加入四甲氧基 矽烷及水，混成物中Si-0-Si網狀鍵結及-SiOH吸收峰隨著 含量增加而增加（圖3(B)-(F))，顯示四甲氧基矽烷大部份轉 變爲矽石（Si02)結構，少部份爲-SiOH基。另外，混成物 6A光譜圖中（圖3(A))出現一較狹窄的Si-0-Si吸收峰，表示 其矽原子均勻分佈在混成物中。然而，其他混成物的 Si-0-Si吸收峰會隨著矽含量的增加而變寬，表示已經水 -12 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 483909 雜 Α7 Β7 五、發明說明（1 Q ) (20G1年12月修正) 解的四甲氧基矽烷縮合形成三度空間的Si-0-Si網狀鍵 結。另外，一般言，醯亞胺五圓環的FT-IR吸收位置在1782 和1724 cm·1，本實驗羰基（C = 0)的吸收位置（1 778和1718 crrf1)略微往短波長偏移，表示矽烷醇基（Si-OH)與聚醯亞 胺的羰基（C = 0)有氫鍵形成。 利用29Si NMR交叉極化光譜探討四甲氧基矽烷 (丁M〇S)與聚石夕氧院醯亞胺水解一縮合形成混成物的反應 結果’如圖4。不同反應組成的對照可以瞭解反應參數、 四甲氧基矽烷、水對最後分子結構的影響，圖4(A)僅加入 適量的水，未加入四甲氧基矽烷；圖4(B)-(D)分別加入30、 50及70重量％的四甲氧基矽烷及固定的莫耳比例水/四甲 氧基矽烷=6;圖4(E)-(F)固定加入50重量％的四甲氧基矽 烷及改變莫耳比例水/四甲氧基矽烷=8和1 0。純的3-胺基 丙基甲基二氧乙基矽烷及四甲氧基矽烷反應物29Si NMR 光譜分別只有在-5.8及-78.6 ppm單一吸收峰，而光譜（A) 出現二個吸收峰，表示存在二種不同矽電子環境，分別爲 D1(-9_6 ppm)及 D2(-20.4 ppm)，相對比例爲 28.6/71.4(表 2)，顯示混成物6A在縮合過程大部份彤成二度空間的D2 網狀結構，此結果亦可說明爲何混成物6A的FT-IR光譜中 Si-0-Si( 1080 cm_1)振動吸收峰較其它混成物窄小的原 因。 混成物6A-30、6A-50和6A-70的29Si NMR光譜（圖 3.5(B)-(D))出現四個吸收峰，分別爲D2(-16_8ppm)、 Q2(-91.4ppm)、Q3(-100.4ppm)及 Q4(-108ppm)，表示四 -13 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) -ί · I I I I I I J ^ ·1,1111111 經濟部智慧財產局員工消費合作社印製 483909 Α7 Β7 (2001年12月修正） 五、發明說明（Π ) 種不同的矽電子環境存在，而D2及0^(1 = 2,3,4)分別屬於 矽氧烷鏈段及矽石網狀結構中矽原子環境（圖2)。各混成 物29Si NMR光譜的化學位移及相對比例整理如表2。 表2、混成物的29Si CP/MAS NMR光譜 化學位移(ppm) 相對比例(％) 漏勿 D1 D2 Q2 Q3 Q4 D1 D2 Q2 Q3 Q4 6Α -9.6 -20.4(687)3 - - - 28.6 71.4 - - - 6Α-30 -16.8(677) -91.5 -100.5 -108.0 0 38.6 7.1 29.7 24.6 6Α-50 -16.6(663) -91.2 -100.5 -108.0 0 23.6 7.7 38.2 30.4 5Α-70 -17.1(760) -91.4 -100.3 -107.7 0 11.6 10.2 46.4 31.8 8Α-50 -16.7(709) -91.2 -100.2 -107.5 0 21.9 64 38.9 32.8 10Α-50 -16.2(701) -91.8 -100.7 -107.6 0 21.5 6.1 39.3 33.1 3括弧內數據表示29Si NMR光譜波峰半高寬（〃 1/2) 由表2結果發現混成物加入四甲氧基矽烷後，在水 解-縮合過程中D1吸收峰消失了，而D2吸收峰面積則隨著 TMOS含量增加而減少，相反地Q2、Q3及Q4吸收峰面積 則增加（圖4. (B)-(D))，顯示更多的矽石網狀結構形成，而 以Q3形態佔優勢，Q4形態次之。另外’網狀聚矽氧烷醯 亞胺-矽石混成物與塊狀聚矽氧烷醯亞胺共聚物的化學位 移有明顯差異，且前者波峰半高寬^ 1/2(663〜760 Hz)則遠 大於後者（97〜153 Hz)，此結果顯示網狀結構抑制矽氧烷 -14 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — —--— — I! -------μ,· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 483909 A7 B7 (2001年12月修正) 修正9〇U9V. Description of the invention (9) (Amended in December 2001) Structural analysis of the interpenetrating mesh type compound (please read the precautions on the back before filling this page) Interpenetrating mesh type polysiloxane-imide-silica compound The theoretical structure of matter is shown in Figure 2. In the mixture 6A, two siloxane bonds and one methyl group are bonded to each silicon atom to form a two-dimensional network structure (Dj; i = 1 or 2). Other mixtures are due to the silanol group (Si-OH) formed by the hydrolysis of 3-aminopropylmethyldioxyethylsilane and tetramethoxysilicon after the addition of tetramethoxysilane. Further polycondensation formed a three-dimensional network structure (D2 and Qh 2 9 i = 2,3,4). The results were confirmed by FTIR and Si NMR spectra. Figure 3 shows the FT-IR (KB0) spectrum of the mixture of different tetramethoxysilane and water content. Results All the mixtures showed characteristic absorption peaks of fluorene imine: 1778 cm_1 (fluorene imine C = 0 symmetrical tensile vibration ), 1718 cm_1 (Amine C = 0 asymmetric tensile vibration), 1500 crn ^ (benzene ring absorption peak), printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 382 cm_1 (CN tensile vibration), 1080 cnrT1 ( Si-0-Si ring asymmetric tensile vibration), 720 crrT1 (bending imine C = 0 out of plane bending vibration). In the figure, two absorption peaks at 3200-3700 cm 1 and 950 cm 1 indicate the 卩"1 ^^ on the 0 & 0 (^ 3 and tetramethoxysilane are hydrolyzed to form a silanol group (-SiOH), and the -SiOH group is further hydrolyzed to form 3 -0-Si (1080 crrT1) Therefore, it is inferred that when tetramethoxysilane and water are added when the mixture reacts, the Si-0-Si network bond and -SiOH absorption peak in the mixture increase with increasing content (Fig. 3 (B)-(F )), Showing that most of the tetramethoxysilane is converted to silica (SiO2) structure, and a small part is -SiOH group. In addition, the spectrum of the mixture 6A (Figure 3 (A)) shows a narrower The Si-0-Si absorption peak indicates that the silicon atoms are evenly distributed in the mixture. However, the Si-0-Si absorption peaks of other mixtures will widen as the silicon content increases, indicating that the water has been -12-this paper Standards are applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 483909 Miscellaneous A7 B7 V. Description of the invention (1 Q) (Amended in December 20G1) The solution of tetramethoxysilane is condensed to form three-dimensional Si -0-Si network bonding. In addition, in general, the FT-IR absorption positions of the fluorene imine rings are 1782 and 1724 cm · 1, and the absorption positions of the carbonyl group (C = 0) (1 778 and 1718) crrf1) is slightly shifted to a short wavelength, indicating that the silane group (Si-OH) and the carbonyl group (C = 0) of polyimide have hydrogen bonds. The 29Si NMR cross-polarization spectrum is used to explore the tetramethoxysilane (butane Mos) and polyisocyanate hydrolyzate imine hydrolysis and condensation to form a mixture 'as shown in Figure 4. Comparison of different reaction composition can understand the effect of reaction parameters, tetramethoxysilane, water on the final molecular structure Fig. 4 (A) only added a proper amount of water, without adding tetramethoxysilane; Fig. 4 (B)-(D) added 30 and 50, respectively And 70% by weight of tetramethoxysilane and fixed mole ratio water / tetramethoxysilane = 6; Figure 4 (E)-(F) fixed addition of 50% by weight of tetramethoxysilane and changing the mole Proportion water / tetramethoxysilane = 8 and 10. The pure 29-NMR spectra of pure 3-aminopropylmethyldioxyethylsilane and tetramethoxysilane reactants are only -5.8 and -78.6 ppm, respectively. Absorption peak, and the spectrum (A) shows two absorption peaks, indicating the existence of two different silicon electronic environments, D1 (-9_6 ppm) and D2 (-20.4 ppm), the relative ratio is 28.6 / 71.4 (Table 2), It is shown that the mixture 6A mostly forms a two-dimensional D2 network structure during the condensation process. This result can also explain why the Si-0-Si (1080 cm_1) vibration absorption peak of the mixture 6A is more than other The reason for the narrow mixture. The 29Si NMR spectra (Figure 3.5 (B)-(D)) of the mixtures 6A-30, 6A-50, and 6A-70 showed four absorption peaks, which were D2 (-16_8ppm), Q2 (-91.4ppm), and Q3. (-100.4ppm) and Q4 (-108ppm), which means four-13-This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back before filling this page)- ί · IIIIIIJ ^ · 1,1111111 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483909 Α7 Β7 (Amended in December 2001) V. Description of Invention (Π) Different silicon electronic environments exist, and D2 and 0 ^ (1 = 2,3,4) belong to the silicon atom environment in the siloxane segment and the silica mesh structure (Figure 2). The chemical shifts and relative proportions of the 29Si NMR spectra of each mixture are summarized in Table 2. Table 2. 29Si CP / MAS NMR spectral chemical shift (ppm) of the mixture (relative ratio) (%) D1 D2 Q2 Q3 Q4 D1 D2 Q2 Q3 Q4 6Α -9.6 -20.4 (687) 3---28.6 71.4-- -6Α-30 -16.8 (677) -91.5 -100.5 -108.0 0 38.6 7.1 29.7 24.6 6Α-50 -16.6 (663) -91.2 -100.5 -108.0 0 23.6 7.7 38.2 30.4 5Α-70 -17.1 (760) -91.4- 100.3 -107.7 0 11.6 10.2 46.4 31.8 8Α-50 -16.7 (709) -91.2 -100.2 -107.5 0 21.9 64 38.9 32.8 10Α-50 -16.2 (701) -91.8 -100.7 -107.6 0 21.5 6.1 39.3 33.1 3 Data in brackets It indicates that the peak width at half maximum of the 29Si NMR spectrum (〃 1/2). From the results in Table 2, it was found that after the tetramethoxysilane was added to the mixture, the absorption peak of D1 disappeared during the hydrolysis-condensation process, and the area of the absorption peak of D2 followed TMOS. The content increased and decreased, while Q2, Q3, and Q4 absorption peak areas increased (Figure 4. (B)-(D)), showing that more silica network structure was formed, and the Q3 form was dominant, and the Q4 form Followed by. In addition, there is a significant difference in the chemical shifts between the reticular polysiloxane-imine-silica mixture and the block polysiloxane-imide copolymer, and the peak width at half maximum of the former ^ 1/2 (663 ~ 760 Hz ) Is much larger than the latter (97 ~ 153 Hz). This result shows that the reticular structure inhibits siloxane-14-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — — — — —- -— — I! ------- μ, · (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483909 A7 B7 (Amended in December 2001) Amendment 9 〇U9
本导《 I 補充 五、發明說明（12 ) 鏈段的運動性，使得光譜波峰半高寬（〃 1/2)遠大於塊狀共 聚物。 混成物8A-50和10A-50的29Si NMR光譜（圖4(E)-(F))與6 A-50相似，但是當水/四甲氧基矽烷莫耳比例增加 時，D2及Q3吸收峰面積減少，而Q4吸收峰相對比例則增 加，此結果可能是因爲四甲氧基矽烷和水之間的水解與縮 合反應較完全所致。再從光譜圖來看，純四甲氧基矽烷反 應物的吸收峰（-78.6 ppm)並不存在，表示四甲氧基矽烷完 全轉變爲矽石（Si02)結構並與混成物形成共價鍵結.。有機 相與無機相間形成共價鍵結的推論，可由表2中Q4的化 學位移（-107.5〜-108.0 ppm)偏移標準矽石網狀結構吸收 (-110 ppm)的結果證實。 互穿網型混成物熱性質分析 混成物在空氣下的熱重損失分析圖（T G A)如圖5，其 重量損失主要有兩個階段，恰如其熱重損失微分圖（DTG) 出現兩個波峰。T G A圖中3 5 0 °C前之連續重量損失，主要 是由於加熱過程中甲醇與水的裂解，而其結果主要是溶膠 -凝膠反應過程有不完全的現象。400-550°C和550-640°C 二個階段的裂解分別屬於矽氧烷有機鏈和醯亞胺鏈段的 裂解，而800°C時的殘餘物爲矽石（silica)，且其殘餘量與 四甲氧基矽烷（TMOS)含量成正比。從資料中發現混成物熱 氧化裂解的第一階段最大重量損失速率溫度（T1m)與殘餘 量隨矽石（Si02)結構含量增加而增加，但是其第二階段最 -15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — — — — — — in--— It---------^ (請先閱讀背面之注意事項再填寫本頁) 483909 Α7 Β7 修正軌 丨衣年Λ 4 補充 五、發明說明（13 ) (2001年】2月修正) 大重量損失速率溫度（T2m)與矽石（Si02)結構含量無關，且 大約是在64CTC左右。另外，混成物8A-50和10A-50的 裂解特性和6A-50類似，結果表示混成物矽氧烷鏈段的熱 氧化裂解受矽石（Si02)結構影響。 混成物在氮氣下的熱重損失如圖6，利用多次高斯函 數分析，發現其熱重損失微分曲線在400°C以上有三階段 的重量損失。混成物6A的三個階段最大重量損失速率溫 度在 417°C (T1m)、548°C (T2m)及 624°C (T3m)，分別爲矽氧 烷有機鏈、D1結構及醯亞胺鏈段的裂解。値得注意的是當 四甲氧基矽烷摻入混成物後，T2m增加且隨矽含量增加而 增加，此結果可能是因爲混成物中Qi結構的形成，且其 Qi鏈段的裂解溫度接近T3m。另外，混成物的裂解速率 (dWt/dt)亦隨矽含量增加而減少，此結果表示矽石（Si02) 結構增加了混成物的熱安定性。 藉由以上實施例及詳細描述會發現，由於在本發明製 備聚矽氧烷醯亞胺-矽石混成物的方法中’係利用帶有兩端 含矽烷的聚醯胺酸來達成。該矽烷末端又各具有兩個可水 解的烷氧基，因此，藉由本方法能提高有機相與無機相間 的相均勻性，以解決習知技藝中相分離現象所帶來的負面 影響。儘管本發明和其優點都作了詳細描述’仍應理解這 裡可以做出各種變化、替換和變換，但並沒有離開由申請 專利範圍附屬項所限定的思路和範圍。 -16- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I--I--|~ 裳· —--I !-訂-----------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製Supplement to this guide "I. V. Description of the invention (12) The motility of the chain segments makes the full width at half maximum (〃 1/2) of the spectral peaks much larger than the block copolymer. The 29Si NMR spectra of the mixtures 8A-50 and 10A-50 (Figures 4 (E)-(F)) are similar to 6 A-50, but when the water / tetramethoxysilane mole ratio increases, D2 and Q3 absorb The peak area decreases and the relative proportion of the Q4 absorption peak increases. This result may be due to the complete hydrolysis and condensation reaction between tetramethoxysilane and water. From the spectrogram, the absorption peak (-78.6 ppm) of the pure tetramethoxysilane reactant does not exist, indicating that the tetramethoxysilane is completely transformed into the silica (Si02) structure and forms a covalent bond with the mixture. Knot ... The corollary of the formation of covalent bonds between the organic and inorganic phases can be confirmed by the chemical shift (-107.5 ~ -108.0 ppm) of Q4 in Table 2 shifted from the standard silica network structure absorption (-110 ppm). Thermal properties analysis of the interpenetrating mesh-type mixture in air Figure 2 shows the thermal weight loss analysis (TGA) of the mixture in air. Its weight loss mainly has two stages, just as its thermal weight loss differential graph (DTG) shows two peaks. . The continuous weight loss before 350 ° C in the T G A chart is mainly due to the decomposition of methanol and water during heating, and the result is mainly an incomplete phenomenon in the sol-gel reaction process. 400-550 ° C and 550-640 ° C two stages of cracking belong to the cleavage of the siloxane organic chain and the fluorene imine segment, respectively, and the residue at 800 ° C is silica, and the residual The amount is directly proportional to the content of tetramethoxysilane (TMOS). From the data, it was found that the maximum weight loss rate temperature (T1m) and residual amount of the first stage of thermal oxidative cracking of the mixture increased with the increase in the structure content of silica (SiO2), but the maximum of the second stage was -15. Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — in --— It --------- ^ (Please read the notes on the back before filling this page) 483909 Α7 Β7 modified track 丨 Year of clothing Λ 4 Supplement V. Description of the invention (13) (2001 revised in February) The large weight loss rate temperature (T2m) has nothing to do with the structure content of silica (Si02), and it is about 64CTC . In addition, the cracking characteristics of the mixtures 8A-50 and 10A-50 are similar to that of 6A-50. The results show that the thermal oxidative cracking of the siloxane segments of the mixture is affected by the structure of silica (Si02). The thermogravimetric loss of the mixture under nitrogen is shown in Figure 6. Using multiple Gaussian function analysis, it was found that the differential curve of thermogravimetric loss has a weight loss of three stages above 400 ° C. The maximum weight loss rate of the three phases of the mixture 6A is 417 ° C (T1m), 548 ° C (T2m), and 624 ° C (T3m), which are the siloxane organic chain, the D1 structure and the fluorene imine segment, respectively. Of cracking. It should be noted that when tetramethoxysilane is added to the mixture, T2m increases and increases with the increase in silicon content. This result may be due to the formation of Qi structure in the mixture, and the cracking temperature of the Qi segment is close to T3m. . In addition, the cracking rate (dWt / dt) of the mixture also decreases with increasing silicon content. This result indicates that the silica (SiO2) structure increases the thermal stability of the mixture. From the above examples and detailed description, it will be found that, in the method for preparing a polysiloxane-imine-silica mixture according to the present invention ', this is achieved by using a polyamidic acid having a silane containing both ends. The silane ends each have two hydrolyzable alkoxy groups. Therefore, the phase uniformity between the organic phase and the inorganic phase can be improved by this method, so as to solve the negative effects caused by the phase separation phenomenon in the conventional art. Although the present invention and its advantages have been described in detail ', it should be understood that various changes, substitutions and alterations can be made here without departing from the ideas and scope defined by the appended items of the scope of patent application. -16- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) I--I-- | ~ 裳 · ---- I! -Order ----------- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs